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Nitrogen Donors in Organometallic Chemistry and Homogeneous Catalysis
Author(s) -
Togni Antonio,
Venanzi Luigi M.
Publication year - 1994
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.199404971
Subject(s) - chemistry , hydrosilylation , catalysis , frustrated lewis pair , enantioselective synthesis , allylic rearrangement , homogeneous catalysis , organic chemistry , alkylation , aldol reaction , organometallic chemistry , coupling reaction , reactivity (psychology) , lewis acids and bases , combinatorial chemistry , medicine , alternative medicine , pathology
Homogeneous catalysis has been responsible for many major recent developments in synthetic organic chemistry. The combined use of organometallic and coordination chemistry has produced a number of new and powerful synthetic methods for important classes of compounds in general and for optically active substances in particular. For this purpose, complexes with optically active ligands have been used, most of them coordinating through phosphorus. More recent developments have highlighted the use of “nitrogen‐donors”, particularly as they are easily obtained from the “chiral pool”. However, the remarkable achievements in this area have been based on an empirical approach. This article attempts to bridge the gap between the synthetic and the coordination chemist. The first section discusses the rates of formation and dissociation of complexes with nitrogen donors, their relationship to the rates of product formation, and presents the factors which induce homolytic cleavage of MC bonds. It also provides a summary of the main types of organometallic complexes formed by metal centers coordinated to nitrogen donors and their reactivity patterns. The second section highlights the most significant, homogeneously catalyzed reactions involving complexes with nitrogen ligands. Foremost among them are the asymmetric aspects of hydrogenation (particularly those involving boranes as reducing agents), hydrosilylation, cyclopropanations, Diels‐Alder reactions, aldol condensations, alkylation of aldehydes, conjugate addition reactions, Grignard cross‐coupling reactions, allylic alkylations, oxidation reactions, olefin epoxidations, and di‐hydroxylation of olefins.